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Operative Dentistry, 2009, 34-5, 551-557

Nanohybrid Resin Composites:


Nanofiller Loaded
Materials or Traditional
Microhybrid Resins?

RR Moraes • LS Gonçalves • AC Lancellotti


S Consani • L Correr-Sobrinho • MA Sinhoreti

Clinical Relevance
Under clinical conditions, nanohybrid resin composites may not perform comparable to
nanofilled materials.

SUMMARY may perform similarly to nanofilled or microhy-


Nanohybrid resin composites present conven- brid resins. The current study investigated the
tional particles to be mixed with nanomeric properties of nanohybrid resins (TPH3, Grandio,
fillers and, therefore, it is unknown whether they Premise, Concept Advanced) in comparison with
a nanofilled (Supreme XT) and a microhybrid
*Rafael Ratto de Moraes, DDS, MS, PhD, professor, Department
(Z250) composite. The inorganic fillers were char-
of Restorative Dentistry, School of Dentistry, UFPel, Brazil acterized by SEM/EDS analysis. Diametral ten-
sile strength (DTS), surface roughness before and
Luciano de Souza Gonçalves, DDS, MS, PhD student,
Department of Restorative Dentistry, Dental Materials after toothbrush abrasion, Knoop Hardness
Division, Piracicaba Dental School, UNICAMP, Brazil (KHN), water sorption and solubility were evalu-
ated. The data were separately analyzed by
Ailla Carla Lancellotti, DDS, MS, PhD student, Department of
Restorative Dentistry, Dental Materials Division, Piracicaba ANOVA and the Student-Newman-Keuls’ tests
Dental School, UNICAMP, Brazil (p<0.05). The results of all analyses were materi-
Simonides Consani, DDS, PhD, professor, Department of
al-dependent. Noticeable differences in filler size
Restorative Dentistry, Dental Materials Division, Piracicaba and shape were detected among the materials.
Dental School, UNICAMP, Brazil Supreme XT generally showed higher DTS and
Lourenço Correr-Sobrinho, DDS, MS, PhD, professor, KHN compared to all the nanohybrids and also
Department of Restorative Dentistry, Dental Materials showed lower surface roughness before and after
Division, Piracicaba Dental School, UNICAMP, Brazil toothbrush abrasion compared to most of the
Mário Alexandre Sinhoreti, DDS, MS, PhD, professor, materials tested. Similar results were generally
Department of Restorative Dentistry, Dental Materials detected for the nanohybrids compared with the
Division, Piracicaba Dental School, UNICAMP, Brazil microhybrid material. In conclusion, the nanohy-
*Reprint request: Rua Goncalves Chaves 457, Pelotas, RS brid resins generally presented inferior proper-
96015-560, Brazil; e-mail: moraesrr@gmail.com ties compared with the nanofilled composite and
DOI: 10.2341/08-043-L either similar or slightly better properties com-

Pedro Augusto Senem - senem.pedroaugusto@gmail.com - CPF: 115.478.529-76


552 Operative Dentistry

pared to the microhybrid material. Under clini- erties;2-3,5 finer particle size results in less interparticle
cal conditions, nanohybrid resins may not per- spacing, more protection of the softer resin matrix and
form similarly to nanofilled materials. less filler plucking.12-13 Nonetheless, little is known as
regards the properties of nanohybrid resin composites.
INTRODUCTION Turssi and others,13 for instance, reported that, in terms
Resin-based restoratives are increasingly being used in of wear and fatigue resistance, nano-structured compos-
dentistry, mainly because of their esthetic quality and ites may perform either similarly or comparatively
good physical properties. A variety of dental composites worse than microfilled materials, and Yesil and others14
that could be used in both anterior and posterior areas reported that nanofillers might not significantly
is available for clinical use, presenting a wide range of improve wear resistance compared with microhybrid
organic and inorganic components that may affect both and microfilled composites.
their handling characteristics and clinical service. The The current study evaluated the properties of com-
introduction of well-dispersed inorganic particles into a mercial nanohybrid resin composites (TPH3, Grandio,
resin matrix has been shown to be extremely effective Premise, Concept Advanced) and compared them with
for improving the performance of polymer composites.1-3 nanofilled (Filtek Supreme XT) and microhybrid (Filtek
The fillers used in dental resins directly affect their Z250) materials in an effort to identify whether nanohy-
radiopacity, properties, wear resistance and elastic mod- brids should be classified as nanofiller-loaded materials
ulus.3-5 Therefore, resin composites have usually been or traditional microhybrid composites. The hypothesis
classified according to filler features, such as type, dis- tested was that nanohybrid materials would be shown
tribution or average particle size. to have properties similar to those of traditional micro-
In addition to traditional microhybrid and microfilled hybrid, and not of nanofilled composites.
materials, nanofilled and nanohybrid composites were
more recently introduced in an endeavor to provide a METHODS AND MATERIALS
material presenting high initial polishing combined Resin Composites Tested
with superior polish and gloss retention.3,5-10 The resin composites evaluated in the current study
Nevertheless, while nanofilled composites use nanosized and their compositions are shown in Table 1.
particles throughout the resin matrix,9 nanohybrids Nanohybrids: TPH3 (Dentsply Caulk, Milford, DE,
take the approach of combining nanomeric and conven- USA), Grandio (VoCo, Cuxhaven, Germany), Premise
tional fillers,11 and this characteristic is similar to micro- (Kerr, Orange, CA, USA) and Concept Advanced
hybrid composites. Therefore, one can speculate that (Vigodent, Rio de Janeiro, RJ, Brazil); nanofilled: Filtek
nanohybrids may still suffer from the loss of large parti- Supreme XT (3M ESPE, St Paul, MN, USA); microhy-
cles, as microhybrids do, and it is questionable whether brid: Filtek Z250 (3M ESPE). All the materials were of
they are really innovative materials and whether they shade A2 or corresponding color. Although classification
should be defined as nanofiller-loaded resins or tradi- criteria among the different manufacturers may vary,
tional microhybrid composites instead.12 the authors of the current study classified all materials
It is known that the shape, amount and size of the par- presenting range of fillers size above 100 nm as
ticles reinforcing the composite might affect their prop- “nanohybrids.”

Table 1: Materials Used in This Study


Resin Composite Manufacturer Classification* Resin Phase** Filler**
Filtek Z250 3M ESPE Microhybrid Bis-GMA, UDMA, Zirconia, silica
Bis-EMA, TEGDMA (0.01–3.5 µm, 75 wt%)
Filtek Supreme XT 3M ESPE Nanofilled Bis-GMA, UDMA, Zirconia, silica
Bis-EMA, TEGDMA (5–20 nm, 78.5 wt%)
TPH3 Dentsply Caulk Nanohybrid Bis-GMA, Bis-EMA, TiO2, silica, Ba-B-F-
TEGDMA Al-Si glass
(0.02–1 µm, 75 wt%)
Grandio VoCo Nanohybrid Bis-GMA, UDMA, Silica, glass ceramic
TEGDMA (0.02–1 µm, 87 wt%)
Premise Kerr Nanohybrid Bis-EMA, TEGDMA Prepolymer, silica, Ba
glass (0.02–0.4 µm,
84 wt%)
Concept Advanced Vigodent Nanohybrid Bis-GMA, UDMA Silica, Ba-Al-Si glass
(0.01–2 µm, 77.5 wt%)
*Although classification criteria among different manufacturers may vary, the authors of the current study classified all materials presenting range of fillers size above 100 nm as “nanohybrids.”
**Information provided by the manufacturers.
Bis-GMA: bisphenol-A glycidyl dimethacrylate; UDMA: urethane dimethacrylate; Bis-EMA: bisphenol-A ethoxylated dimethacrylate; TEGDMA: triethylene glycol dimethacrylate.

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Moraes & Others: Nanohybrid vs Nanofilled Resin Composites 553

Filler Characterization bristles per tuft). The specimens were completely


The unpolymerized resin phase of each composite was immersed in slurry of dentifrice (Colgate Classic,
removed by dissolving 0.2 g of each material in 100% Hollywood, FL, USA) and distilled water (1:2 weight
acetone and additionally in chloroform for 24-hour peri- ratio). In total, 30,000 strokes (complete forward and
ods. The remaining filler particles were placed in 100% reverse movement) were performed at a frequency of 4
ethanol; the suspension was smeared on a metal stub Hz. The specimens were then cleaned with a one-
and dried at 37°C for 24 hours. The materials were minute air/water spray, followed by a 10 minute ultra-
coated with gold and examined by scanning electron sonic bath, and surface roughness was determined
microscopy (SEM—JSM5600LV; JEOL Inc, Peabody, again. The data were submitted to Repeated Measures
MA, USA) to investigate their filler morphology and ANOVA and Student-Newman-Keuls’ test (p<0.05).
size. An additional batch of fillers was coated with car- Hardness
bon and analyzed using energy dispersive x-ray spec- Hardness readings were performed on the non-brushed
troscopy (EDS, Noran Instruments, Middleton, WI, bottom diameter of the samples that were retrieved
USA) to assess the elemental composition and percent- from the toothbrush abrasion using an indenter (HMV-
age distribution of the elements present in the filler 2; Shimadzu Corp, Tokyo, Japan). The bottom surfaces
particles. were polished with medium, fine and superfine alu-
Diametral Tensile Strength minum oxide discs (Sof-Lex system, 3M ESPE), and the
Five cylindrical specimens (4 mm diameter x 2 mm samples were ultrasonically cleaned in distilled water
thick) per resin composite were obtained by placing the for 10 minutes. For each specimen, five indentations
materials into elastomer molds and light-curing them were performed under a load of 50 g for 15 seconds. The
for 20 seconds from both the top and bottom surfaces Knoop Hardness number (KHN, kg/mm2) for each spec-
using a quartz-tungsten-halogen curing device imen was recorded as the average of the five readings.
(XL2500, 3M ESPE—700 mW/cm2). After storage in dis- The data were submitted to ANOVA and the Student-
tilled water at 37°C for 24 hours, the specimens were Newman-Keuls’ test (p<0.05).
wet-polished with 1200-grit SiC abrasive papers. The Water Sorption and Solubility
diametral tensile strength (DTS) test was performed in Five cylindrical specimens (4 mm in diameter x 1 mm
a mechanical testing machine (model 4411; Instron, thick) were obtained for each material following the
Canton, MA, USA) at a crosshead speed of 0.5 same procedures described for the DTS test. After cal-
mm/minute. The specimens were positioned vertically culating the volume (V, in mm3) of the specimens, they
on the base of the machine and subjected to compres- were stored in a desiccator at 37°C and repeatedly
sive loading until failure. Means were calculated in weighed after 24-hour intervals using an analytical bal-
MPa and the data submitted to ANOVA and Student- ance (JK-180; Chyo Balance Corp, Tokyo, Japan) accu-
Newman-Keuls’ test (p<0.05). rate to 0.1 mg until a constant mass (m1) was obtained.
Toothbrush Abrasion The samples were then individually placed in sealed
Eight conical specimens per composite (5 mm top diam- vials, immersed in distilled water and stored at 37°C.
eter x 4 mm bottom diameter x 1 mm thick) were After seven days, the surface water of the specimens
obtained using brass molds, following the same photo- was removed by blotting with absorbent paper and
activation protocol for the DTS. After storage in dis- waving the specimen in the air for 10 seconds. The
tilled water for 24 hours at 37°C, the top surfaces were weighing procedures were repeated, by which m2 was
polished with medium, fine and superfine aluminum recorded. The specimens were then placed in the desic-
oxide discs (Sof-Lex system, 3M ESPE), and the sam- cator again, at 37°C, and reweighed until a constant dry
ples were ultrasonically cleaned in distilled water for 10 mass (m3) was obtained. Water sorption (Wsp) and solu-
minutes. Baseline surface roughness readings were bility (Wsl), given in µg/mm3, were calculated as follows:
taken on the top diameter of the samples by rotating Wsp=(m2–m3)/V; Wsl=(m1–m3)/V. The data were sepa-
them clockwise at random angles through a surface rately submitted to ANOVA and the Student-Newman-
profilometer (Surfcorder SE1700, Kosaka Lab, Tokyo, Keuls’ test (p<0.05).
Japan) equipped with a diamond stylus (0.5 µm tip
radius) accurate to 0.01 µm. The stylus traversed across RESULTS
the diameter of each sample three times, and the mean Results for the EDS analysis are shown in Table 2.
roughness parameter for each specimen (Ra, µm) was While both the nanofilled and microhybrid resin com-
recorded as the mean of the three readings. posites presented Si and Zr as the main components of
Toothbrush abrasion was carried out on a multi-sta- the inorganic fillers, the nanohybrids presented Si and
tion brushing device. The top diameter of each sample Ba as main components and also presented a small
was brushed using a soft, nylon-bristle toothbrush amount of Al. SEM pictures of the fillers for each com-
(Johnson & Johnson, Langhorne, PA, USA, 32 tufts, 60 posite are shown in Figures 1 and 2. The microhybrid

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554 Operative Dentistry

Table 2: Elemental Composition (wt%) of the Inorganic Phase of Each Material Z250 presented
Resin Composite Ba Al Si Zr
r o u n d - shaped
small and medium
Z250 - - 66% 34%
particles, while the
Supreme XT - - 57% 43%
n a n o f i l l e d
TPH
3
57% 6% 37% -
Supreme XT was
Grandio 11% 12% 77% - shown to have
Premise 56% 5% 39% - round-shaped nan-
Concept Advanced 49% 7% 44% - oclusters. For the
Values are relative to the mass fraction of each component present in the filler particles. nanohybrids, TPH3
presented irregu-
lar-shaped small
Table 3: Means (Standard Deviations) for DTS, KHN, Wsp and Wsl and medium parti-
Resin Composite DTS (MPa) 2
KHN (kg/mm ) Wsp (µg/mm )
3
Wsl (µg/mm )
3
cles, Grandio pre-
Z250 53.7 (5.1) ab 69.6 (6.1) b 30.7 (4.9) a 1.9 (1.2) a sented very large
Supreme XT 58.0 (11.0) a 72.4 (7.4) b 29.1 (5.1) a 2.9 (2.1) a irregular-shaped
TPH
3
53.4 (4.8) ab 54.9 (2.6) d 26.4 (6.4) a 2.9 (1.9) a particles mixed
Grandio 54.6 (11.7) ab 111.7 (13.6) a 15.1 (5.3) b 3.1 (1.8) a with medium
Premise 40.1 (11.1) b 62.4 (6.2) c 18.1 (4.5) ab 5.1 (2.5) a
fillers, Premise
showed very large
Concept Advanced 38.8 (7.1) b 44.8 (2.4) e 17.3 (4.3) b 3.1 (2.2) a
irregular-shaped
Means followed by distinct letters in the same column are significantly different at p<0.05.
clusters formed by
small particles and
Concept presented large irregular-shaped
clusters, also formed by small fillers. Results
for DTS and KHN are shown in Table 3.
Supreme XT showed the highest DTS values,
which were significantly higher than those of
Premise (p=0.032) and Concept Advanced
(p=0.026) but similar to those of the other
composites (p≥0.063). As regards hardness,
almost all the materials presented significant-
ly different values when compared with each
other: Grandio > Z250 and Supreme XT >
Premise > TPH3 > Concept Advanced
(p≤0.022).
Results for water sorption and solubility are
shown in Table 3. Z250, Supreme XT and
TPH3 presented significantly higher sorption
than Grandio and Concept Advanced
(p≤0.012), which were similar. Premise pre-
sented intermediary sorption values, with no
significant differences compared with any
other resin composite (p≥0.068). On the other
hand, no significant differences in solubility
were detected among all composites (p≥0.183).
Results for the surface roughness analysis are
shown in Table 4. Before toothbrush abrasion,
Supreme XT, Premise and Concept Advanced
showed significantly smoother surfaces com-
pared with the other resin composites
(p<0.001), which were similar (p≥0.583). After
Figure 1. SEM pictures of inorganic fillers. Figures 1A and 1B Z250–microhybrid: round- toothbrushing, the results were: Supreme XT
shaped small and medium particles are predominant; Figures 1C and 1D–Supreme XT and Premise < Concept Advanced < TPH3 and
nanofilled: round-shaped clusters are observed, although the magnification is not sufficient Z250 < Grandio (p≤0.042). Comparing the
to accurately observe the individual nanosized particles; Figures 1E and 1F–TPH3 nanohy- times before and after abrasion, Z250 and
brid: irregular-shaped small and medium particles are present.

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Moraes & Others: Nanohybrid vs Nanofilled Resin Composites 555

Table 4: Means (Standard Deviations) for Surface Roughness Before and After Toothbrush large clusters formed by
Abrasion small particles (Premise,
Surface Roughness (Ra, µm) Concept), while others pre-
Resin Composite sented large fillers (TPH3,
Before After
Z250 0.24 (0.09) A,a 0.27 (0.08) A,b
Grandio). The nanotechnolo-
gy concept refers to a field of
Supreme XT 0.09 (0.02) B,b 0.12 (0.02) A,d
applied science whose theme
TPH 3
0.25 (0.08) A,a 0.30 (0.09) A,b
is the control of matter in the
Grandio 0.24 (0.04) B,a 0.36 (0.04) A,a atomic and molecular scale,
Premise 0.08 (0.01) B,b 0.11 (0.02) A,d generally 100 nm or small-
Concept Advanced 0.09 (0.01) B,b 0.16 (0.01) A,c er.1,3,5 Therefore, the size of
Means followed by distinct capital letters in the same line, and small letters in the same column, are significantly different at p<0.05. the fillers observed for the
nanohybrid resins could per
se be a reason to not refer to
them as nano-structured materials, as
microhybrid composites may also mix nano-
sized particles with large fillers. In addition,
the results of the EDS analysis showed that
the composition of the fillers presented in
nanohybrids is the same as almost all of the
traditional hybrids, namely Ba-Al-Si glass
fillers.3-5,12
The shape of the fillers presented in the
nanohybrids was also different when com-
pared with the nanofilled material (Figures
1 and 2). The properties of nanoparticles and
the resulting nanocomposites are size- and
shape-dependent.2 In order to produce inor-
ganic nanoparticles, the materials are either
mechanically crushed in a conventional
manner or synthesized from precursor com-
pounds by controlling the crystal growth
kinetics.1 The top-down approach is when
macroscopic particles are downsized by
physical means, such as mechanical grind-
ing or high energy milling,1 which seems to
be the approach for the nanohybrids tested
here. However, there are limiting factors to
this approach, as particles become irregular-
ly-shaped and sizes below 500 nm can hard-
ly be generated.1 On the other hand, the bot-
tom-up approach starts at the other end:
materials and phases are generated by phys-
Figure 2. SEM pictures of the inorganic fillers. Figures 2A and 2 B–Grandio nanohybrid: ical or chemical means from precursor com-
very large, irregular-shaped particles are present, mixed with medium fillers; Figures 2C
pounds forming nanoscale fillers,1 allowing
and 2D–Premise nanohybrid: very large, irregular-shaped clusters were detected, formed
by small particles shown in the magnification; Figures 2E and 2F–Concept Advanced the production of round-shaped fillers less
nanohybrid: large, irregular-shaped clusters are also present, and the small fillers that form than 100 nm in diameter, such as those
it can be observed in the detail. observed for the nanofilled resin.
With regard to the properties of the
TPH3 showed no significant differences (p≥0.431),
restoratives, the results were generally dependent on
whereas all the other materials presented significantly
the material evaluated, especially with regard to filler
rougher surfaces after toothbrushing (p≤0.006).
features. Nanofilled Supreme XT showed significantly
DISCUSSION higher DTS than Premise and Concept, which were
precisely the only two nanohybrids whose fillers were
The current results indicate that, with regard to filler clusters rather than large individual particles. This
morphology, some nanohybrid composites presented suggests that the entanglement between the resin

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556 Operative Dentistry

components and the nanofillers is better for Supreme itself. Characteristics of the chemical structure of
XT, enhancing the three-dimensional microstructure monomers, especially with regard to the potential for
of the composite and improving its mechanical hydrogen bonding and polar interactions, present a
strength. The shape of the nanofillers in Supreme XT strong influence on the hydrophilicity of the polymer
may also explain this result, as Kim and others15 network. The filler features would present a significant
reported that composites with round particles may effect only if the amount of the fillers dispersed
present increased mechanical strength. This is further throughout the resin phase were different among com-
evidence that nanohybrids may not behave similarly to posites, which is not the case. Furthermore, no signifi-
nanofills. Furthermore, similar DTS values were cant differences in solubility were observed among the
observed for Supreme XT compared with the remain- composites tested. This result indicates that the cur-
ing restoratives, which might be related to the large rent resin composites are virtually insoluble in water,
particles presented by the other materials. although it has been demonstrated that the effects of
The results indicated no trend towards the size or water on dental polymers might be affected by aging.4
shape of fillers affecting hardness. Indeed, all materi- All evaluations showed a material-dependent effect.
als generally presented different results in comparison The current results indicate that the behavior of
with one another. Grandio, for instance, presented the nanohybrid resin composites is more closely related to
highest KHN values, probably because of presenting that of microhybrid than nanofilled materials.
large particles and the highest filler content. The sim- Therefore, is seems that nanohybrids are not innova-
ilar results detected for Z250 and Supreme XT indicat- tive materials and that the “new” classification is prob-
ed that, not only the filler particles, but also the com- ably related to marketing strategies. This is clinically
ponents of the resin phase themselves might interfere relevant, considering that professionals could opt for
with hardness. The microhybrid and nanofilled com- using a nanohybrid resin in order to obtain high polish
posites tested here present the same organic matrix retention with time, but this effect is uncertain.
components in spite of the noticeable differences in Notwithstanding, the addition of small particles form-
filler size. Similarity in resin components might pro- ing large clusters seems to be the most efficient way to
duce similar polymer network structures and therefore obtain the retention of high smoothness, but the shape
similar hardness results when the filler loading is sim- of the particles forming the cluster may also affect the
ilar. outcomes. Nonetheless, the results of the current study
When evaluating the surface smoothness before do not take into account the effects that pH changes,
abrasion, the nanofilled material and both nanohy- salivary enzymes and mechanical fatigue might have
brids presenting clusters showed lower surface rough- on clinical performance. The clinical evaluation of
ness than all the other materials, which indicates a nanohybrids compared with microhybrids and
beneficial effect of the presence of small fillers forming nanofills would more properly indicate differences in
clusters. However, the great theoretical advantage of performance among these materials.
nanocomposites should be that they retain their pol- CONCLUSIONS
ished surfaces over the course of time. After toothbrush
abrasion, the nanofilled composite presented lower The nanohybrid resins tested generally presented infe-
surface roughness than all the other materials, except rior properties compared with the nanofilled composite
for Premise. Concept also showed lower Ra values after and either similar or slightly better properties com-
toothbrushing compared with all the remaining mate- pared with the microhybrid material.
rials. These outcomes again indicate that, in general,
nanohybrids may not perform in a similar manner to Acknowledgements
nanofilled composites, but their performance is similar The authors thank Dentsply Caulk and Vigodent for donation of
to, or sometimes slightly better than that of microhy- their materials and to Mr Adriano Martins for assistance with
brids. In corroboration, a recent study observed that, SEM/EDS analysis.
while nanofills could be expected to withstand the
wear caused by brushing, nanohybrids had higher
roughness levels.10 Another point to be highlighted is (Received 13 October 2008)
that the presence of clusters formed by small particles
seems to reduce the surface roughness of the materials References
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Moraes & Others: Nanohybrid vs Nanofilled Resin Composites 557

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